Phenyl pyrid(-one or-thione) compounds which are intermediates

ABSTRACT

A compound of formula (I) ##STR1## wherein R 1 , R 2 , R 4  and R 5  are independently selected from hydrogen, halogen, lower alkyl optionally substituted by halogen, lower alkoxy optionally substituted by halogen and lower alkenyl optionally substituted by halogen; 
     R 3  is halogen, amino, mono- or di(lower alkyl)-amino, lower alkyl substituted by halogen, lower alkoxy optionally substituted by halogen and lower alkenyl optionally substituted by halogen provided that R 3  is not monochloro or monobromo-methyl; 
     R 6  is oxygen or sulphur; 
     R 7  and R 10  are independently selected from hydrogen, halogen, lower alkyl optionally substituted by halogen, lower alkoxy optionally substituted by halogen, and lower thioalkoxy optionally substituted by halogen; and 
     R 8  is hydrogen, halogen, optionally substituted lower alkyl, optionally substituted lower alkoxy, optionally substituted lower thioalkoxy, cyano, nitro, optionally substituted oximino, optionally substituted lower alkenyl, optionally substituted aryloxy, optionally substituted amino or S(O)nR 11  wherein n is 0, 1 or 2 and R 11  is optionally substituted lower alkyl; 
     R 9  is hydrogen, or lower alkyl optionally substituted by halogen, lower alkenyl optionally substituted by halogen or CO 2  R 12  wherein R 12  is lower alkyl optionally substituted by halogen; provided that R 1 , R 2  R 3 , R 4  and R 5  are not all hydrogen; and further provided that when R 3  is trifluoromethyl and R 1  and R 5  are halogen, R 2  and R 4  are not both hydrogen, or R 7 , R 8 , R 9  and R 10  do not comprise from one to four halogen or trihalomethyl substitutents.

This is a divisional of U.S. application Ser. No. 07/089,823, filed Aug.27, 1987, now U.S. Pat. No. 4,866,078, issued Sept. 12, 1989.

This invention relates to novel aryl pyridones useful as insecticidalagents.

The invention provides a compound of formula (I) ##STR2## wherein R¹,R², R⁴ and R⁵ are independently selected from hydrogen, halogen, loweralkyl optionally substituted by halogen, lower alkoxy optionallysubstituted by halogen and lower alkenyl optionally substituted byhalogen;

R³ is halogen, amino, mono- or di-(lower alkyl)-amino, lower alkylsubstituted by halogen, lower alkoxy optionally substituted by halogenand lower alkenyl optionally substituted by halogen provided that R³ isnot monochloro or monobromo-methyl;

R⁶ is oxygen or sulphur;

R⁷ and R¹⁰ are independently selected from hydrogen, halogen, loweralkyl optionally substituted by halogen, lower alkoxy optionallysubstituted by halogen, and lower thioalkoxy optionally substituted byhalogen; and

R⁸ is hydrogen, halogen, optionally substituted lower alkyl, optionallysubstituted lower alkoxy, optionally substituted lower thioalkoxy,cyano, nitro, optionally substituted oximino, optionally substitutedlower alkenyl, optionally substituted aryloxy, optionally substitutedamino or S(O)nR¹¹ wherein n is 0, 1 or 2 and R¹¹ is optionallysubstituted lower alkyl;

R⁹ is hydrogen, or lower alkyl optionally substituted by halogen, loweralkenyl optionally substituted by halogen or CO₂ R¹² wherein R¹² islower alkyl optionally substituted by halogen; provided that R¹, R², R³,R⁴ and R⁵ are not all hydrogen; and further provided that when R³ istrifluoromethyl and R¹ and R⁵ are halogen, R² and R⁴ are not bothhydrogen, or R⁷, R⁸, R⁹ and R¹⁰ do not comprise from one to four halogenor trihalomethyl substitutents.

As used herein the term "lower" used in relation to alkyl or alkoxygroups means groups having from 1 to 6 carbon atoms preferably from 1 toto 3 carbon atoms and when used in relation to alkenyl groups meansgroups having from 2 to 6 carbon atoms, preferably 2 or 3 carbon atoms.The term "aryl" includes phenyl.

Suitably R¹, R², R³, R⁴ and R⁵ are selected from hydrogen, halogen suchas fluorine, chlorine or bromine; lower alkyl such as methyl or ethyl,lower alkoxy, such as methoxy or halo(lower)alkyl such astrifluoromethyl.

Preferred examples of R¹ and R⁵ include hydrogen, fluorine, chlorine andbromine.

Preferably both R¹ and R⁵ are chlorine.

Preferred examples of R² and R⁴ include hydrogen, halogen in particular,fluorine, lower alkyl such as methyl or ethyl and lower alkoxy such asmethoxy.

Preferred examples of R³ include halogen such as fluorine and chlorine,amino and halo lower alkyl such as trifluoromethyl.

Preferably R⁶ is oxygen.

Examples of suitable halogen atoms for R⁷, R⁸ and R¹⁰ include bromo.

Preferably R⁷ and R¹⁰ are both hydrogen.

Examples of R⁸ include hydrogen, halo, lower alkyl optionallysubstituted by halo or hydroxy; cyano; nitro; oximino optionallysubstituted by lower alkyl, aryl, lower alkenyl or aralkyl wherein thearyl portion is optionally substituted with halogen or nitro; loweralkenyl optionally substituted by halogen or cyano; amino; or S(O)R¹¹wherein n is 0, 1, or 2 and R¹¹ is lower alkyl optionally substituted byhalogen such as fluorine.

Specific examples of R⁸ include hydrogen, iodo, methyl, hydroxymethyl,chloromethyl, difluoromethyl, dichloromethyl, thiomethyl, ethoxyimino,t-butyloximino, p-nitrobenzyloxyimino, phenoxyimino,pentafluorobenzyloximino, prop-2-enyloxyimino, 2,2-dichloroethenyl,2-cyanoethenyl, ethynyl or S(O)CF₃.

Preferably R⁸ is hydrogen or cyano.

Suitable groups R⁹ include halo(lower)alkyl, branched chain lower alkyl,halo(lower)alkenyl, or a lower carboxylic ester group.

Examples of suitable groups R⁹ include trifluoromethyl,2,2-di-bromoethenyl, ethoxycarbonyl and tert-butyl.

Specific examples of compounds of formula I are set out in Table I.

                                      TABLE I                                     __________________________________________________________________________    COMPOUND                                                                              R.sup.1                                                                         R.sup.2                                                                         R.sup.3                                                                             R.sup.4                                                                           R.sup.5                                                                           R.sup.6                                                                         R.sup.7                                                                         R.sup.8           R.sup.9                                                                            R.sup.10                 __________________________________________________________________________     1      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H H                 CO.sub.2 Et                                                                        H                         2      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H H                 CHCBr.sub.2                                                                        H                         3      H H CF.sub.3                                                                            H   H   O H H                 CF.sub.3                                                                           H                         4      Cl                                                                              H CF.sub.3                                                                            CH.sub.3                                                                          Cl  O H H                 CF.sub.3                                                                           H                         5      Cl                                                                              H CF.sub.3                                                                            C.sub.2 H.sub.5                                                                   Cl  O H H                 CF.sub.3                                                                           H                         6      F F CF.sub.3                                                                            OCH.sub.3                                                                         F   O H H                 CF.sub.3                                                                           H                         7      F F CF.sub.3                                                                            F   F   O H H                 CF.sub.3                                                                           H                         8      F F F     F   F   O H H                 CF.sub.3                                                                           H                         9      F H CF.sub.3                                                                            H   OCH.sub.3                                                                         O H H                 CF.sub.3                                                                           H                        10      Cl                                                                              H CF.sub.3                                                                            H   OCH.sub.3                                                                         O H H                 CF.sub.3                                                                           H                        11      F H CF.sub.3                                                                            H   F   O H H                 tC.sub.4 H.sub.9                                                                   H                        12      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H H                 CHF.sub.2                                                                          H                        13      Cl                                                                              H CHF.sub.2                                                                           H   Cl  O H H                 CF.sub.3                                                                           H                        14      Cl                                                                              H CHCl.sub.2                                                                          H   Cl  O H H                 CF.sub.3                                                                           H                        15      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H SCF.sub.3         CF.sub.3                                                                           H                        16      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H (CH.sub.2).sub.3 CH.sub.3                                                                       CF.sub.3                                                                           H                        17      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H                                                                                ##STR3##         CF.sub.3                                                                           H                        18      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H                                                                                ##STR4##         CF.sub.3                                                                           H                        19      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H                                                                                ##STR5##         CF.sub.3                                                                           H                        20      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CNOCH.sub.3       CF.sub.3                                                                           H                        21      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H                                                                                ##STR6##         CF.sub.3                                                                           H                        22      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CNOC(CH.sub.3).sub.3                                                                            CF.sub.3                                                                           H                        23      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CNOCH.sub.2 CHCH.sub.2                                                                          CF.sub.3                                                                           H                        24      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CNOCH.sub.2C.sub.6 F.sub.5                                                                      CF.sub.3                                                                           H                        25      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CH.sub.3          CF.sub.3                                                                           H                        26      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H S(O)CF.sub.3      CF.sub.3                                                                           H                        27      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CHCCl.sub.2       CF.sub.3                                                                           H                        28      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H SCH.sub.3         CF.sub.3                                                                           H                        29      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CN                CF.sub.3                                                                           H                        30      Br                                                                              H CF.sub.3                                                                            H   Br  O H CN                CF.sub.3                                                                           H                        31      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H NO.sub.2          CF.sub.3                                                                           H                        32      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CH.sub.2 OH       CF.sub.3                                                                           H                        33      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CH.sub.2 Cl       CF.sub.3                                                                           H                        34      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H                                                                                ##STR7##         CF.sub.3                                                                           H                        35      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CHF.sub.2         CF.sub.3                                                                           H                        36      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CHCl.sub.2        CF.sub.3                                                                           H                        37      Cl                                                                              H CF.sub.3                                                                            H   Cl  O H CHCHCN            CF.sub.3                                                                           H                        38      Cl                                                                              H NH.sub.2                                                                            H   Cl  O H H                 CF.sub.3                                                                           H                        39      Cl                                                                              H Cl    H   Cl  O H H                 CF.sub.3                                                                           H                        40      Cl                                                                              H CH.sub.2 F                                                                          H   Cl  O H H                 CF.sub.3                                                                           H                        41      Cl                                                                              H (CH.sub.3).sub.2 CF                                                                 H   Cl  O H H                 CF.sub.3                                                                           H                        __________________________________________________________________________

The compounds of formula I may be prepared by reacting a compound offormula (II): ##STR8## wherein R^(1'), R^(2'), R^(3'), R^(4') and R^(5')are equivalent to R¹, R², R³, R⁴ and R⁵ respectively as hereinbeforedefined or a precursor thereof and R¹³ is a leaving group such as halo,with a compound of formula (III): ##STR9## where R^(7'), R^(8'), R^(9')and R^(10') are equivalent to R⁷, R⁸, R⁹ and R¹⁰ respectively ashereinbefore defined or a precursor thereof and thereafter if necessarycarrying out one or more of the following steps:

(i) converting a group R^(1'), R^(2'), R^(3'), R^(4'), R^(5'), R^(7'),R^(8'), R^(9'), R¹⁰ to R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹ or R¹⁰respectively; or

(ii) converting the carbonyl group to ═S.

The reaction is suitably carried out in the presence of a solvent and abase. The base may be for example an alkali metal hydride, an alkalimetal alkoxide or an alkali metal carbonate, and the solvent may be ahydrocarbon solvent, such as petroleum ether, an alcohol or an aproticpolar solvent such as dimethylformamide or dimethylacetamide. Suitablehalo groups R¹³ include fluoro, chloro, bromo or iodo and if necessaryan appropriate catalyst such as a crown ether or copper can be addeddepending upon the precise nature of R¹³. Further details of theprocesses for preparation of the compounds may be ascertained from theExamples set out hereinafter.

Optional step (ii) above may be carried out by reacting compounds offormula (I) wherein R⁶ is oxygen with a thiolating agent such asphosphorus pentasulphide. The reaction is suitably carried out in anorganic solvent such as pyridine at elevated temperatures of from 50° C.to 150°.

As used herein the term "precursor" applies to a group which can beconverted to a chemical group R¹, R², R³, R⁴, R⁵, R⁷, R⁸, R⁹ or R¹⁰ bystandard chemical techniques. A particularly useful precursor of thistype is the formyl group as R^(8') or R^(9'). This group can beconverted to various oxime, optionally substituted alkyl, optionallysubstituted alkenyl, optionally substituted alkynyl, and cyano groups R⁸as illustrated hereinafter.

For example compounds of formula (I) where R⁹ is optionally substitutedalkenyl can be prepared by reacting a compound of formula (IV) ##STR10##wherein R¹, R², R³, R⁴, R⁵, R⁷, R⁸ and R¹⁰ are as hereinbefore definedwith an appropriate substituted alkane in the presence of zinc andtriphenyl phosphine under conventional Wittig reaction conditions.

An additional useful precursor of this type is the nitro group, inparticular as R³ ' as this can be converted to amino as illustratedhereinafter.

A further useful precursor group, particularly for the R^(3') group isethoxycarobnyl. This group can be readily converted to various hydroxyalkyl groups such as hydroxy methyl or 1-methyl-1-hydroxy ethyl bystandard techniques such as by reduction or using Grignard reactions.The hydroxy alkyl groups can be converted directly to compounds of theinvention, for example by halogenation or they may be converted to asecond precursor such as formyl which is discussed above.

Descriptions of reactions using these precursors is given by way ofillustration in the Examples hereinafter.

Intermediates of formula (V) ##STR11## where R¹, R², R³, R⁴, R⁵ R⁷ andR¹⁰ are as defined in relation to formula (I),

R¹⁶ and R¹⁷ are selected from R⁸ and R¹⁰ respectively or formyl and R¹⁸is R³ is hereinbefore defined, nitro or C₁₋₆ alkoxycarbonyl or loweralkyl substituted by hydroxy provided that at least one of R¹⁶, R¹⁷ andR¹⁸ is not R⁸, R¹⁰ or R³ respectively are novel and as such form anaspect of the invention.

Compounds of formula (I) can be converted to other compounds of formula(I) having different substituent R groups by conventional methods ifdesired. For example, when one of R¹, R², R³, R⁴ or R⁵ is fluoro, it canbe converted to an alkoxy group by reaction with an appropriate alkoxyanion of formula R¹⁴ O⁻ where R¹⁴ is lower alkyl. Anions of formula R¹⁴O⁻ may be prepared by dissolving sodium metal in an alcohol of formulaR¹⁴ OH suitably at moderate temperatures of from 0° to 100° C.,preferably at room temperature.

Compounds of formula (II) are largely known compounds or they can beproduced from known compounds by conventional methods. However compoundsof formula (II) where R³ is trifluoromethyl and R² or R⁴ is lower alkyloptionally substituted by halogen are novel and as such form part of theinvention.

These compounds can be prepared by reacting a compound of formula (VI)##STR12## wherein R¹, R⁵ and R¹³ are as hereinbefore defined with acompound of formula R¹⁵ -R¹⁶ where R¹⁵ is a lower alkyl group and R¹⁶ ishalogen such as iodine in the presence of a base such as n-butyllithium.

Compounds of formula (IV) can be prepared by oxidation of a compound offormula (VII) ##STR13## wherein R¹, R², R³, R⁴, R⁵, R⁷, R⁸ and R¹⁰ areas hereinbefore defined. The oxidation is suitably carried out using anoxidising agent for example using Swern oxidation procedures. Thereaction is suitably carried out in an organic solvent such asdichloromethane in the presence of a base low temperatures for exampleof from -100° C. to 0° C. are suitably employed.

Compounds of formula (VII) can be prepared by reduction of a compound offormula (I) wherein R⁹ is CO₂ R¹² using a reducing agent such as lithiumborohydride. The reaction is suitably carried out in an inert organicsolvent such as tetrahydrofuran at temperatures of form 0°-150° C.

Certain compounds of formula (III) are also novel and these also formpart of the invention. Therefore in a further aspect of the inventionthere is provided a compound of formula (IIIA): ##STR14## wherein R¹⁹ istrihalomethyl

and R²⁰ is an electrophilic group R^(8') as hereinbefore defined.

Particular examples of R¹⁹ includes trifluoromethyl.

Particular examples of R²⁰ include nitro, lower thioalkoxy optionallysubstituted by halogen such as trifluoromethylthio, formyl, and loweralkyl as methyl or butyl optionally substituted by halogen.

Compounds of formula (IIIA) wherein R²⁰ is an electrophilic group otherthan nitro can be prepared by reacting a compound of formula (VIII)##STR15## wherein R¹⁹ is as hereinbefore defined with a base and acompound ##STR16## wherein R²¹ is a leaving group such as halogen.Examples of such reactions are given hereinafter.

The base used in the reaction is preferably a combination of sodiumhydride followed by t-butyllithium. Suitably 2 equivalents of base areemployed. The reaction is preferably carried out in an inert organicsolvent such as tetrahydrofuran.

Compounds of formula (IIIA) wherein R¹⁸ is nitro can be prepared bynitration of a compound of formula (VIII) under standard conditions.

Other compounds of formula (III) and compounds of formula (VIII) areeither known compounds or they can be produced from known compounds byconventional methods.

The compounds of formula (I) may be used to combat and controlinfestations of insect pests and also other invertebrate pests, forexample, acarine pests. The insect and acarine pests which may becombated and controlled by the use of the invention compounds includethose pests associated with agriculture (which term includes the growingof crops for food and fibre products), horticulture and animalhusbandry), forestry, the storage of products of vegetable origin, suchas fruit, grain and timber, and also those pests associated with thetransmission of diseases of man and animals.

In order to apply the compounds to the locus of the pests they areusually formulated into compositions which include in addition to theinsecticidally active ingredient or ingredients of formula I suitableinert diluent or carrier materials, and/or surface active agents. Thecompositions may also comprise another pesticidal material, for exampleanother insecticide or acaricide, or a fungicide, or may also comprisean insecticide synergist, such as for example dodecyl imidazole,safroxan, or piperonyl butoxide.

The compositions may be in the form of dusting powders wherein theactive ingredient is mixed with a solid diluent or carrier, for examplekaolin, bentonite, kieselguhr, or talc, or they may be in the form ofgranules, wherein the active ingredient is absorbed in a porous granularmaterial for example pumice.

Alternatively the compositions may be in the form of liquid preparationsto be used as dips or sprays, which are generally aqueous dispersions oremulsions of the active ingredient in the presence of one or more knownwetting agents, dispersing agents or emulsifying agents (surface activeagents).

Wetting agents, dispersing agents and emulsifying agents may be of thecationic, anionic or non-ionic type. Suitable agents of the cationictype include, for example, quaternary ammonium compounds, for examplecetyltrimethyl ammonium bromide. Suitable agents of the anionic typeinclude, for example, soaps, salts of aliphatic monoesters of sulphuricacid, for example sodium lauryl sulphate, salts of sulphonated aromaticcompounds, for example sodium dodecylbenzenesulphonate, sodium, calciumor ammonium lignosulphonate, or butylnaphthalene sulphonate, and amixture of the sodium salts of diisopropyl- and triispropylnaphthalenesulphonates. Suitable agents of the non-ionic type include, for example,the condensation products of ethylene oxide with fatty alcohols such asoleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonyl phenol and octyl creson. Other non-ionic agents are thepartial esters derived from long chain fatty acids and hexitolanhydrides, the condensation products of the said partial esters withethylene oxide, and the lecithins.

The compositions may be prepared by dissolving the active ingredient ina suitable solvent, for example, a ketonic solvent such as diacetonealcohol, or an aromatic solvent such as trimethylbenzene and adding themixture so obtained to water which may contain one or more knownwetting, dispersing or emulsifying agents.

Other suitable organic solvents are dimethyl formamide, ethylenedichloride, isopropyl alcohol, propylene glycol and other glycols,diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene,xylenes and trichloroethylene, N-methyl-2-pyrrolidone andtetrahydrofurfuryl alcohol (THFA).

The compositions which are to be used in the form of aqueous dispersionsor emulsions are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient or ingredients,the said concentrate to be diluted with water before use. Theseconcentrates are often required to withstand storage for prolongedperiods and after such storage, to be capable of dilution with water toform aqueous preparations which remain homogenous for a sufficient timeto enable them to be applied by conventional spray equipment. Theconcentrates may contain 10-85% by weight of the active ingredient oringredients. When diluted to form aqueous preparations such preparationsmay contain varying amounts of the active ingredient depending upon thepurpose for which they are to be sued. For agricultural or horticulturalpurposes, an aqueous preparation containing between 0.0001% and 0.1% byweight of the active ingredient (approximately equivalent to from 5-2000g/ha) is particularly useful.

In use the compositions are applied to the pests, to the locus of thepests, to the habitat of the pests, or to growing plants liable toinfestation by the pests, by any of the known means of applyingpesticidal compositions, for example, by dusting or spraying.

The compounds of the invention may be the sole active ingredient of thecomposition or they may be admixed with one or more additional activeingredients such as insecticides, insecticide synergists, herbicides,fungicides or plant growth regulators where appropriate.

Suitable additional active ingredients for inclusion in admixture withthe compounds of the invention may be compounds which will broaden thespectrum of activity of the compounds of the invention or increase theirpersistence in the location of the pest. They may synergise the activityof the compound of the invention or complement the activity for exampleby increasing the speed of effect, improving knockdown or overcomingrepellency. Additionally multi-component mixtures of this type may helpto overcome or prevent the development of resistance to individualcomponents.

The particular insecticide, herbicide or fungicide included in themixture will depend upon its intended utility and the type ofcomplementary action required. Examples of suitable insecticides includethe following:

a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin,cyhalothrin in particular cyhalothrin, biphenthrin, fenpropathrin,cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox,natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin,prallethrin and5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate;

b) Organophosphates such as profenofos, sulprofos, methyl parathion,azinphos-methyl, demoton-s-methyl, heptenophos, thiometon, fenamiphos,monocrotophos, profenophos, triazophos, methamidophos, dimethoate,phosphamidon, malathion, chloropyrifos, phosalone, fensulfothion,fonofos, phorate, phoxim, pyrimiphosmethyl, fenitrothion or diazionon;

c) Carbamates (including aryl carbamates) such as pirimicarb,cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan,beniocarb, fenobucarb, propoxur or oxamyl;

d) Benzoyl ureas such as triflumeron, or chlorofluazuron;

e) Organic tin compounds such as cyhexatin, fenbutatin oxide,azocyclotin;

f) Macrolides such as avermectins or milbemyins, for example such asavamectin, avermectin, and milbemycin;

g) Hormones such as pheromones;

h) Organochlorine compounds such as benzene hexachloride, DDT, chlordaneor dieldrin.

i) Amidines, such as chlordimeform or amitraz.

In addition to the major chemical classes of insecticide listed above,other insecticides having particular targets may be employed in themixture if appropriate for the intended utility of the mixture. Forinstance selective insecticides for particular crops, for examplestemborer specific insecticides for use in rice such as cartap orbuprofezin can be employed. Alternatively insecticides specific forparticular insect species/stages for example ovo-larvicides such aschofentezine, flubenzimine, hexythiazox and tetradifon, moltilicidessuch as dicofol on propargite, acaricides such as bromopropylate,chlorobenzilate, or growth regulators such as hydramethylon, cyromazin,methoprene, chlorofluazuron and diflubenzuron may also be included inthe compositions.

Examples of suitable insecticide synergists for use in the compositionsinclude piperonyl butoxide, sesamax, and dodecyl imidazole.

Suitable herbicides, fungicides and plant-growth regulators forinclusion in the compositions will depend upon the intended target andthe effect required.

An example of a rice selective herbicides which can be included ispropanil, an example of a plant growth regulator for use in cotton is"Pix", and examples of fungicides for use in rice include blasticidessuch as blasticidin-S.

The ratio of the compound of the invention to the other activeingredient in the composition will depend upon a number of factorsincluding type of target, effect required from the mixture etc.

However in general, the additional active ingredient of the compositionwill be applied at about the rate as it is usually employed, or at aslightly lower rate if synergism occurs.

The compounds of formula I and compositions comprising them have shownthemselves active against a variety of insect and other invertebratepests. They are particularly useful in controlling public health pestssuch as flies and cockroaches. Certain compounds of formula (I) andcompositions comprising them are useful against pests in rice crops,such as rice hoppers. They may also be active against organophosphateand pyrrethroid resistant strains of pests such as houseflies (Muscadomestica). They may be effective in combating both susceptible andresistant strains of the pests in their adult, larval and intermediatestages of growth, and may be applied to the infested host animal bytopical, oral or parenteral administration. The compounds also havenematocidal activity.

The following Examples illustrate various aspects of this invention. Inthe Preparations and Examples the products were usually identified andcharacterised by means of nuclear magnetic resonance spectroscopy andinfra red spectroscopy. In each case where a product is specificallynamed its spectral characteristics are consistent with the assignedstructure.

EXAMPLE 1

This Example illustrates the preparation of 4-ethoxycarbonyl-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-2-pyridone (Compound1 in Table I).

Sodium hydride (10.7 g of a 50% dispersion in mineral oil, 0.23 mol) waswashed with diethyl ether in a dry flask flushed with nitrogen. Dimethylformamide (110 ml) was added and the mixture gently stirred at roomtemperature whilst 4-carboethoxy-2-pyridone (35.1 g, 0.21 mol) was addedportionwise, being rinsed into the flask with a further volume ofdimethylformamide (20 ml).

After 15 minutes, when gas evolution had ceased, 3,5-dichloro-4-fluorobenzotrifluoride (100 g, 0.43 mol) was added, the reaction was heated at90° C. for 3-5 hours and left to stand at room temperature for 16 hours.

A few drops of ethanol were added and the mixture stirred for fiveminutes before being poured into water (1000 ml) and extracted withethyl acetate. The extract was well washed with water, dried overmagnesium sulphate and evaporated in vacuo. The residue was washed withan ethyl acetate/petrol mixture to give the required compound (30 g)which could be purified further by recrystallization from a mixture ofethyl acetate and petrol to give white crystals (mp 135.7°-137.3° C.); δ(d₆ -acetone) 8.0 (2H,s), 7.6 (1H,d), 7.2 (1H,d), 6.8 (1H,dd), 4.4(2H,q), 1.4 (3H,t).

EXAMPLE 2

This example illustrates the preparation of4-(2,2-dibromovinyl)-1-(2,6-dichloro-4-trifluoro-methylphenyl)-2-pyridone(Compound 2).

To lithium borohydride (0.32 g, 14.5 mmol) suspended in tetrahydrofuran(10 ml) was added a solution of 4-ethoxy carbonyl-1-2,6dichloro-4-trifluoromethylphenyl)-2-pyridone (Compound 1, 10 g, 26 mmol)in tetrahydrofuran (30 ml). The mixture was heated under reflux for twohours, allowed to cool to room temperature and the solvent removed invacuo. The residue was shaken with water and ethyl acetate, the layersseparated, and the aqueous layer extracted with ethyl acetate. Thecombined organic layers were washed with water, then brine, dried overmagnesium sulphate and evaporated in vacuo to give4-hydroxymethyl-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-2-pyridone asa brown gum (9.2 g) (Compound 13).

The material was not further purified, but dissolved in dichloromethane(30 ml) and used in the next step.

A well-stirred solution of oxalyl chloride (3 ml, 32.5 mmol) indichloromethane (75 ml) was cooled to -60° C. in a dry flask undernitrogen.

A solution of dimethylsulphoxide (5 ml, 65 mmol) in dichloromethane wasrapidly added, keeping the reaction temperature below -50° C. After twominutes the dichloromethane solution of alcohol (13) was added over fiveminutes, and the reaction stirred at -50° to -60° C. for fifteenminutes. Triethylamine (35 ml, 0.25 mol) was then added and after afurther five minutes the cooling bath was removed and the reactionmixture allowed to warm to room temperature. The reaction mixture waspoured into water, the layers separated and the aqueous layer extractedwith dichloromethane. The combined organic layers were washedsequentially with brine 1% hydrochloric acid, 5% sodium carbonate andwater and dried with magnesium sulphate.

The solvent was evaporated in vacuo and the residue chromatographed onsilica with 40% diethyl ether in petrol as eluent to afford1-(2,6-dichloro-4-trifluoromethylphenyl)-4-formyl-2-pyridone as a whitesolid (5.1 g, mp 114.8°-116.7° C.); δ (d₆ -acetone) 10.05 (1H,s), 8.1(2H,s), 7.7 (1H,d), 7.2 (1H,s), 6.75 (1H,d). The aldehyde (1 g, 3 mmol)was added in one portion to a well-stirred mixture of carbontetrabromide (1.97 g, 6 mmol), triphenylphosphine (1.56 g, 6 mmol) andzinc powder (0.39 g, 6 mmol) in dichloromethane (20 ml) which had beenpre-stirred for two minutes. The reaction mixture was heated underreflux for one hour, cooled to room temperature, and poured into water.The organic layers were washed with water, then brine and dried overmagnesium sulphate.

Evaporation in vacuo gave a brown residue which was treated with diethylether, filtered and the filtrate purified by column chromatography onsilica with 1:1 by the careful addition of water (50 ml) and allowed towarm to room temperature. The mixture was poured into water (350 ml) andextracted with ether (2×300 ml). The organic layers were washed wellwith water, dried over magnesium sulphate and the solvent evaporated invacuo. The resulting liquid was distilled in a Kugelrohr apparatus togive the required compound (3.7 g mp 70° C. at 20 mm Hg); δ (CDCl₃) 7.6(1H,d), 2.5 (3H,s).

EXAMPLE 5

3,5-dichloro-2-ethyl-4-fluoro benzotrifluoride was prepared by themethod described in Example 4 using ethyl iodide in place of methyliodide.

EXAMPLE 6

The following compounds were prepared by the method described in Example1 from the appropriate compounds of the formula I (Hal representsfluoro) and formula II.

(i) 1-(2,6-dichloro-4-trifluoromethyl-3-methylphenyl)-4-trifluoromethyl-2-pyridone (Compound 4, Table I) except thatthe reaction was heated at 80° C. for sixteen hours. The compound showedmp: 168°-169° C.; δ (d₆ -acetone) 8.0 (1H,s), 7.8 (1H, dm), 7.0 (1H,m),6.7 (1H,dd), 2.9 (3H,m).

(ii)1-(2,6-dichloro-3-ethyl-4-trifluoromethylphenyl)-4-trifluoromethyl-2-pyridone(Compound 5, Table I) except that the reaction was heated at 90° C. forsixteen hours. The compound showed mp 145°-146° C.; δ (d₆ -acetone) 8.0(1H,s), 7.8 (1H, dm), 7.0 (1H,m), 6.7 (1H,dd), 3.0 (2H,q), 1.24 (2H,t).

(iii)1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-4-trifluoromethyl-2-pyridone(Compound 7, Table I) except that the reaction was heated at 60° C. forfive hours. The compound showed mp 102.6°-103.3° C.; δ (d₆ -acetone)8.05 (1H,d), 7.15 (1H,m) 6.05 (1H,dd).

(iv) 1-(2,3,4,5,6-pentafluorophenyl)-4-trifluoromethyl-2-pyridone(Compound 8, Table I) except that the reaction was heated at 60° C. forfive hours. The compound showed δ (d₆ -acetone) 7.95 (1H, dm), 7.0(1H,m), 6.65 (1H,dd).

(v) 1-(2,6-difluoro-4-trifluoromethylphenyl)-4-tertbutyl-2-pyridone(Compound 11, Table I) except that the reaction was heated at 50° C. forthree hours. The compound showed mp 152.7°-153.0° C.; δ (d₆ acetone/CD₃CN) 7.6 (2H,d), 7.3 (1H,d), 6.5 (2H,M), 1.3 (9H,s).

EXAMPLE 7

This example illustrates the preparation of1-(2,5,6,-trifluoro-3-methoxy-4-trifluoromethylphenyl-4-trifluoromethyl-2-pyridone(Compound 6, Table 1).

1-(2,3,5,6-tetrafluoro-4-trifluoromethylphenyl)-4-trifluoromethyl-2-pyridone (Compound 7, 300 mg, 0.79 mmol) wasadded to a solution made by adding sodium metal (20 mg 0.87 mmol) tomethanol (10 ml). When the mixture had been stirred at room temperaturefor five hours the methanol was evaporated in vacuo, the residue takenup in ethyl acetate, washed with water, dried over magnesium sulphateand evaporated in vacuo to give a yellow oil. The oil was purified bychromatography on silica with 20% diethylether/petrol mixture as eluentto give the requisite compound (140 mg); δ (d₆ -acetone) 7.9 (1H,d), 7.0(1H,m) 6.62 (1H,dd), 4.08 (3H,d).

EXAMPLE 8

The following compounds were prepared by the method described in Example7 from the appropriate compound of formula I:

(i) 1-(2-fluoro-6-methoxy-4-trifluoromethylphenyl-2-pyridone (Compound9, Table I) except that the reaction was stirred at 20° C. for threehours and 50° C. for a further three hours. The compound showed mp140.0°-140.7° C., δ (d₆ -acetone 7.9 (1H, d) 7.50 (1H,s), 7.45 (1H,d),7.00 (1H,m), 6.68 (1H,dd), 4.15 (3H,s).

(ii)1-(2-chloro-6-methyl-4-trifluoromethyl-phenyl)-4-trifluoromethyl-2-pyridone(Compound 10, Table I) except that the reaction was heated under refluxfor eight hours. The compound showed mp 146.6°-147.1° C.; δ (d₆-acetone) 7.93 (1H,d), 7.75 (1H,d), 7.6 (1H,s), 7.59 (1H,s) 6.60(1H,dd), 4.00 (3H,s).

EXAMPLE 9

This Example illustrates the preparation of1-(2,6-dichloro-4-trifluoromethylphenyl)-4-difluoromethyl-2-pyridone(Compound 12, Table I).

A dry flask was flushed with nitrogen and charged with1-(2,6-dichloro-4-trifluoromethyl-phenyl)-4-formyl-2-pyridone (530 mg1.57 mmol) which had been prepared as described in Example 2. The flaskwas cooled to 0° C. in an ice bath and diethylaminosulphur trifluoride(DAST) (0.19 ml, 1.57 mmol) was added slowly dropwise. The cooling bathwas removed and the reaction mixture stirred at ambient temperature fortwo hours before being slowly poured into saturated aqueous sodiumbicarbonate.

The aqueous mixture was extracted with ethyl acetate and the organiclayers washed with water, dried over magnesium sulphate and evaporatedin vacuo to give a black gum which was chromatographed on silica with20% diethylether/petrol mixture as eluant to give the required compound(236 mg, mp 136.5°-137.2° C.); δ (d₆ -acetone) 8.1 (2H,s), 7.7 (1H,d)6.9 (1H,t) 6.8 (1H,m), 6.6 (1H,dd).

EXAMPLE 10

This Example illustrates the preparation of Compound 17 in Table I.

Step A

5-Bromo-4-trifluoromethyl-2-pyridone (25 g) was added portionwise to asuspension of sodium hydride (5.5 g of a 50% suspension in mineral oil)in tetrahydrofuran (250 ml) whereupon hydrogen was evolved. The reactionmixture was cooled to -78° C. and a solution (90 ml) of tertiary-butyllithium (2.6M) in pentane added whilst maintaining the temperature below-55° C. A solution of dry dimethylformamide (40 ml) in tetrahydrofuran(150 ml) at a temperature of -78° C. was added and a thick grey/purplemixture formed. A small amount (ca: 5 mls) ammonium chloride solutionwas then added and the mixture allowed to warm to room temperature. Theresulent yellow solution was partitioned between ammonium chloride (50ml) and ethylacetate and the ethylacetate extracts were discarded. Theaqueous layer was acidified to pH6 using concentrated hydrochloric acidand extracted into ethyl acetate which was washed and dried as describedabove. The ethyl acetate was then removed under reduced pressure and theresultant brown solid was recrystallised from ethyl acetate to give 5formyl-4-trifluoromethyl-2-pyridone (13.3 g).

This compound was reacted with 3,5-dichloro-4-fluorobenzotrifluoridedescribed in Example 1 to give Compound A which was found to be1-(2,6-chloro-4-trifluoromethylphenyl)-5-formyl-5-formyl-4-trifluoromethyl-2-pyridone.

M.P.: 186.9°-188.1° C.

NMR δ (CDCl₃): 9.95 (1H, q); 8.0 (1H, d); 7.8 (2H, s); 7.05 (1H, s).

Step B

Compound A (97 mg) prepared as described above was dissolved in ethanol(3 ml) and water (1 ml) and 2M NaOH solution (2 ml) added. To thismixture was added an excess of O-ethyl hydroxylamine hydrochloride inthe form of an aqueous solution and the pH of the resultant solutionadjusted to 8-9 by the addition of potassium hydroxide pellets withstirring at room temperature. The reaction mixture was heated underreflux for 2 hours and then poured into water, extracted into ether,dried over magnesium sulphate and concentrated under reduced pressure.The product was purified by column chromatography using 30% dietylether/petrol as a diluent to give Compound 17 as a white solid (87 mg).

NMR δ (CDCl₃): 8.55 (s, 1H); 8.10 (s, 1H); 7.79 (s, 2H); 7.35 (s, 1H);7.10 (m, 1H); 7.06 (s, 1h); 4.1-4.3 (m, 2H); 1.3-1.4 (m, 3H).

EXAMPLE 11

The following compounds were prepared in an analogous manner to thatdescribed in Example 10.

    ______________________________________                                        Compound 18                                                                             NMR δ (CDCl.sub.3)                                                                    8.52 (1H, s); 7.72 (2H,                                                       s); 7.40 (1H, m); 7.28                                                        (5H, s); 7.10 (1H, s);                                                        5.10 (2H, s).                                         Compound 19                                                                             NMR δ (CDCl.sub.3)                                                                    8.24 (2H, d); 8.2 (1H,                                                        s); 7.79 (2H, s); 7.71                                                        (1H, s); 7.5 (2H, d);                                                         7.07 (1H, s); 5.24 (2H,                                                       s).                                                   Compound 20                                                                             NMR δ (CDCl.sub.3)                                                                    8.48 (1H, s); 8.10 (1H,                                                       m); 7.88 (2H, s); 7.80                                                        (2H, s); 7.76 (1H, s);                                                        7.30 (1H, m); 7.05 (1H,                                                       s); 3.98 (3H, s); 3.92                                                        (3H, s).                                              Compound 21                                                                             NMR δ (CDCl.sub.3)                                                                    8.46 (1H, s); 7.9 (1H,                                                        s); 7.8 (2H, s); 7.30                                                         (2H, dd); 7.15 (2H, dd);                                                      7.11 (1H, s); 7.05 (1H,                                                       dt).                                                  Compound 22                                                                             NMR δ (CDCl.sub.3)                                                                    8.08 (1H, s); 7.81 (2H,                                                       s); 7.69 (1H, s); 7.06                                                        (1H, s); 1.31 (9H, s).                                Compound 23                                                                             NMR δ (CDCl.sub.3)                                                                    8.15 (1H, s); 7.79 (2H,                                                       s); 7.72 (1H, s); 7.06                                                        (1H, s); 6.00 91H, ddt);                                                      5.29 (1H, dd); 5.23 (1H,                                                      dd); 4.63 (2H, d).                                    Compound 24                                                                             NMR δ (CDCl.sub.3)                                                                    8.10 (1H, s); 7.80 (2H,                                                       s); 7.71 (1H, s); 7.05                                                        (1H, s); 5.21 (2H, s).                                ______________________________________                                    

EXAMPLE 12

This Example illustrates the preparation of Compound 15 in Table I.

A solution of 5-bromo-4-trifluoromethyl-2-pyridone (1 g) intetrahydrofuran (10 ml) was added to a suspension of sodium hydride(0.22 g of a 50% suspension in mineral oil) in tetrahydrofuran (10 ml)whereupon hydrogen was evolved. The mixture was cooled to -75° C. and a7.7M solution of t-butyllithium in pentane (5.35 ml) was added dropwise,keeping the temperature below -60° C. CF₃ SCl gas was condensed into aflask at -78° C. and then distilled into the reaction vessel through acanula. A slightly exothermic reaction took place to give a redsolution. A few drops of ammonium chloride solution were then added toquench the reaction mixture which was then allowed to warm up to roomtemperature. The reaction mixture was partitioned between aqueousammonium chloride and ethylacetate. The organic extracts were washedwith brine, dried over magnesium sulphate and the ethyl acetate removedunder reduced pressure. The remaining orange crystals wererecrystallised using ethyl acetate, and the product reacted with3,5-dichloro-4 -fluorobenzotrifluoride as described in Example 1 to giveCompound 15 as white crystals.

NMR δ (CDCl₃): 7.8 (2H, s); 7.6 (1H, s); 7.1 (1H, s).

EXAMPLE 13

This Example illustrates the preparation of Compound 25 in Table I.

A solution of 5-bromo-4-trifluoromethyl-2-pyridone (1.7 g) intetrahydrofuran (30 ml) was added slowly to a suspension of sodiumhydride (0.37 g of a 50% suspension in mineral oil) in tetrahydrofuranand the solution cooled to -85° C. A 1.56M solution of t-butyllithium inpentane (9.9 ml) was added whilst maintaining the temperature below -80°C. Methyl iodide (5 eq) was then added to the mixture which resulted inan exothermic reaction which raised the temperature to -30° C. Afterstirring for 10 minutes, water was added to the reaction mixture at -50°C. and the pH adjusted to 4 by the addition of aqueous hydrochloricacid. The aqueous reaction mixture was extracted into trichloromethaneand the extracts washed with brine and dried over magnesium sulphate.Trichloromethane was removed under reduced pressure and the remainingsolid recrystallized from a mixture of ethyl acetate and petrol. Theproduct (780 mg) was reacted with 3,5-dichloro-4-fluorobenzotrifluorideas described in Example 1 to give Compound 25.

NMR δ (CDCl₃): 7.8 (2H, s); 7.05 (1H, s); 6.9 (1H, s); 2.1 (3H, t).

Compounds 14, 16 and 28 were prepared in an analogous manner using ICN,n-butylbromide and CH₃ S-SCH₃ respectively in place of methyl iodide inthe Example 13.

    ______________________________________                                        Compound 14                                                                             M.P. 134.6-135.7° C.                                                                 8.3 (1H, s); 8.1 (2H,                                           NMR δ (acetone)                                                                       s); 7.1 (1H, s).                                      Compound 16                                                                             NMR δ (CDCl.sub.3)                                                                    7.8 (2H, s); 7.0 (1H, s);                                                     6.9 (1H, s); 2.55 (2H,                                                        m); 1.5 (4H, m; 0.95 (3H,                                                     m).                                                   Compound 24                                                                             M.P. 115.0-116.4° C.                                                                 8.1 (2H, m); 8.05 (1H,                                          NMR δ (acetone)                                                                       m); 7.05 (1H, m); 2.4                                                         (3H, s).                                              ______________________________________                                    

EXAMPLE 14

This Example illustrates the preparation of Compound 26 in Table I.

Compound 15 (100 mg) prepared as described in Example 12 was dissolvedin dry dichloromethane (2 ml), metachloroperbenzoic acid (43 mg) wasadded portionwise and the mixture heated under reflux for 4 hours. Themixture was then run through a silica column using 10% diethyl ether inpetrol as eluent. Compound 26 was recovered as a white solid (80 mg).

NMR δ (CDCl₃): 8.05 (1H, s); 7.8 (2H, s); 7.1 (1H, s).

EXAMPLE 15

This Example illustrates the preparation of Compound 27 in Table I.

Compound A (0.5 g) prepared as described in Example 10, Step A wasdissolved in dichloromethane (3 ml) and added to a suspension oftriphenyl phosphine (0.65 g), zinc (0.16 g) and carbon tetrachloride(0.38 g) in dichloromethane (2 ml). The mixture was heated under refluxfor 4 hours then added to water and extracted into diethyl ether. Theextracts were washed with brine, dried over magnesium sulphate and thediethyl ether removed under reduced pressure. The remaining buffcoloured solid was run through a silica column using 10% diethylether/petrol as eluent and Compound 27 recovered as a white solid (345mg).

NMR δ (CDCl₃ (: 7.8 (2H, s); 7.4 (1H, m); 7.1 (1H, m); 6.7 (1H, m).

EXAMPLE 16

This Example illustrates the preparation of Compound 29 in Table I.

Compound A (0.5 g) was prepared as described in Example 10 Step A, mixedwith hydroxylamine hydrochloride (0.095 g), sodium formate (0.095 g) and98% formic acid (2 ml) and the mixture was heated under reflux for 4hours. The aqueous mixture was then extracted into diethyl ether and theextracts washed with aqueous sodium bicarbonate solution followed bybrine and dried over magnesium sulphate. The diethyl ether was removedunder reduced pressure leaving a white solid which was purified bycolumn chromatography on a silica column using 20% diethyl ether/petrolto give Compound 29 as a white solid (130 mg).

NMR δ (CDCl₃): 7.8 (2H, s); 7.75 (1H, s); 7.1 (1H, s).

1-(2,6-Dibromo-4-trifluoromethylphenyl)-5-formyl-4-trifluoromethyl-2-pyridone (CompoundB) was prepared in a manner analogous to that described in Example 10Step A but using 3,5-dibromo-4-fluorobenzotrifluoride in the finalcondensation reaction.

Compound 30 was prepared from Compound B in an analogous manner to thatdescribed above for the preparation of Compound 29 from Compound A.

NMR δ (CDCl₃): 8.0 (2H, s); 7.7 (1H, s); 7.1 (1H, s).

EXAMPLE 17

This Example illustrates the preparation of Compound 31 in Table I.

4-Trifluoromethyl-2-pyridone (20 g) was dissolved in concentratedsulphuric acid (100 ml) and the mixture warmed to 35° C. A nitratingmixture comprising concentrated nitric acid (11.1 g) and sulphuric acid(10 ml) was added in stages and the mixture warmed to 65° C. for a totalof 11/2 hours. After this the mixture was poured into ice and a whiteprecipitate formed which was filtered off and the aqueous phaseextracted into ethyl acetate and the extracts washed with brine anddried over magnesium sulphate. The solvent was removed under reducedpressure to give a brown oil. This oil was run through a silica columnusing 5% methanol in dichloromethane as eluent and5-nitro-4-trifluoromethyl-2-pyridone was collected as a white solid.This was reacted with 3,5-dichloro-4-fluorobenzotrifluoride as describedin Example 1 to give Compound 31 as a yellow solid.

M.P.: 144.2°-144.8° C.

NMR δ (CDCl₃): 8.4 (1H, s); 7.8 (2H, s); 7.5 (1H, s).

EXAMPLE 18

This Example illustrates the preparation of Compound 32 in Table I.

Compound A (1 g) prepared as described in Example 10 Step A wassuspended in methanol (10 ml), sodium borohydride (94 mg) was added andthe reaction mixture stirred at room temperature until all the aldehyde(A) had been consumed (TLC: 30% ethylether/petrol eluent).

A yellow precipitate was formed. The reaction mixture was added to brine(100 ml) and extracted into ethyl acetate. The extracts were washed withbrine, dried over magnesium sulphate and the solvent removed underreduced pressure to give Compound 32 as an off white solid.

NMR δ (CDCl₃): 7.7 (2M, s); 7.33 (1H, s); 7.04 (1H, s); 4.67 (2H, s);2.24 (1H, br, s).

EXAMPLE 19

This Example illustrates the preparation of Compound 33 in Table I.

Compound 32 (350 mg) was mixed with triphenyl phosphine (250 mg) andcarbon tetrachloride (6 ml) and the mixture heated under reflux for 10hours after which the reaction mixture was added to water and thenextracted into diethyl ether. The extracts were washed with brine, driedover magnesium sulphate and the solvent removed under reduced pressure.The resultant off-white solid was run through a silica column using 20%diethyl ether in petrol as eluent and Compound 33 obtained as a whitesolid (200 mg).

NMR δ (CDCl₃): 7.8 (2H, s); 7.35 (1H, s); 7.1 (1H, s); 4.55 (2H, s).

EXAMPLE 20

This Example illustrates the preparation of Compound 34 in Table I.

A Wittig reagent was prepared by suspending Ph₃ P⁺ CH₂ Cl Cl⁻ (0.43 g)in dry tetrahydrofuran (10 ml) cooling to -78° C. and adding potassiumt-butoxide (0.30 g) portionwise.

Compound A (0.5 g) (as described in Example 10 Step A) was dissolved intetrahydrofuran (5 ml) and the solution cooled to -78° C.

The Witting reagent was then added to the solution which was stirred for1/2 hour and then allowed to warm to room temperature. The mixture wasadded to water, extracted into diethyl ether and the extracts washedwith brine and dried over magnesium sulphate. After removal of solventunder reduced pressure, the remaining solid was passed down a silicacolumn using 5% diethyl ether in petrol as eluent and the fractionscollected. Compound 34 was obtained by recrystallisation of the productfrom 60-80 petrol as a white solid.

NMR δ (CDCl₃): 7.8 (2H, s); 7.4 (1H, s); 3.0 (1H, m); 3.2 (1H, s).

EXAMPLE 21

This Example illustrates the preparation of Compound 35 in Table I. DAST(0.17 ml) was added to solid Compound A (0.5 g) at 0° C. and the mixturestirred for one hour. A further sample of DAST (1 ml) was added and themixture stirred for two days. It was then diluted with dichloromethane(ca. 3 ml) and added slowly to aqueous sodium bicarbonate solution. Avigorous reaction occurred with effervescence. The aqueous phase wasextracted into dichloromethane, the extracts washed with brine and driedover magnesium sulphate and the solvent removed under reduced pressure.Purification by chromatography using a silica column and 20% diethylether/petrol as eluent yielded Compound 35 as a white solid.

M.P.: 132.0°-132.8° C.

NMR δ (CDCl₃): 7.8 (2H, s); 7.6 (1H, s); 7.1 (1H, s); 6.7 (1H, t).

EXAMPLE 22

This Example illustrates the preparation of Compound 36 in Table I.

Compound A (0.5 g), (described in Example 10 Step A) phosphoruspentachloride (0.28 g) and carbon tetrachloride (3 ml) were refluxedtogether for one hour. The reaction mixture was then added to water,extracted into ethyl acetate and the ethyl acetate extracts washed firstwith sodium bicarbonate and then with brine. After drying over magnesiumsulphate the solvent was removed under reduced pressure and theresultant solid purified by running through a silica column using 20%diethyl ether/petrol as eluent. Compound 36 was obtained as a whitesolid (460 mg).

M.P.: 112°-114° C.

NMR δ (CDCl₃): 7.9 (1H, s); 7.8 (2H, s); 7.0 (1H, s); 6.8 (1H, s).

EXAMPLE 23

This Example illustrates the preparation of Compound 37 in Table I.

The Wittig salt Ph₃ P⁺ CH₂ CN Cl⁻ (0.46 g) was suspended intetrahydrofuran, cooled to -78° C., and potassium t-butoxide (0.153 g)added portionwise. After ensuring complete formation of the anion byallowing the solution to warm to room temperature and stirring for halfan hour, the solution was cooled to -78° C. and added to a solution ofCompound A (0.5 g) in tetrahydrofuran (3 ml) also at -78° C. The mixturewas allowed to warm to room temperature, stirred for one hour and addedto water. The mixture was extracted into diethyl ether and the extractswashed with brine, and dried over magnesium sulphate. The diethyl etherwas removed under reduced pressure and the resulting oil run through asilica column using a 20% diethyl ether/petrol as eluent.

Compound 37 was recovered as a white solid (340 mg).

NMR δ (CDCl₃): 7.9 (1H, s); 7.8 (2H, s); 7.2 (1H, d); 7.1 (1H, s); 5.6(1H, d).

EXAMPLE 24

This Example illustrates the preparation of Compound 39 in Table I.

Step A

Sodium hydride suspension (0.36 g, of a 50% suspension in mineral oil)was washed with 40/60 petrol under nitrogen to remove the oil. Asolution of 4-trifluoromethyl-2-pyridone (1.1 g) dissolved in drydimethylformamide (10 ml) was added dropwise. The reaction mixture wasstirred at room temperature, under nitrogen for 1/2 hour. After thistime 3,5-dichloro-4-fluoro-nitrobenzene (2.0 g) dissolved in drydimethyl-formamide (5 ml) was added in one portion. The reaction mixturewas heated at 100° C. for 41/2 hours, then the reaction temperature wasincreased to 110° C. for a further c.a. 20 hours. After this time, thereaction was cooled and quenched with water. The mixture was acidifiedwith dilute hydrochloric acid and extracted with ethyl acetate (2×50ml). The combined organic extracts were washed with brine (3×30 mls) anddried over magnesium sulphate. The organic layer was then concentratedunder reduced pressure to give a yellow solid. The compound was passeddown a silica column using 4:1 petrol/ether as the eluting solvent, thecompound being eluted very slowly. The fractions containing the productwere confirmed and the solvent removed under reduced pressure. Theresidue was triturated with pentane and collected by filtration underreduced pressure. 1-([2,6-dichloro-4-nitro)phenyl]-4-trifluoroemthyl-2-pyridone was obtained as a white crystalline solid(1.18 g).

NMR δ (CDCl₃): 8.53 (2H, s); 7.81 (1H, d); 6.98 (1H, m); 6.70 (1H, dd).

Step B

A sample of the product of Step A (0.5 g) was suspended in methanol (5ml).

The suspension was added dropwise to a stirred solution of stannouschloride (0.81 g) in concentrated hydrochloric acid (1.3 ml) at roomtemperature. A slightly exothermic reaction was noted after which thereaction mixture was stirred at room temperature for 1 hour, and allowedto stand overnight at room temperature. The mixture was quenched withwater, basified and extracted with ethyl acetate (2×25 ml). The organiclayers were combined and washed with brine (3×30 ml). The acid layer wasthen basified with 10M aqueous sodium hydroxide solution in the presenceof ethyl acetate (30 ml) and the aqueous layer was extracted twice withethyl acetate (2×30 ml). The combined organic layers were dried overmagnesium sulphate and the solvent removed under reduced pressure togive Compound 38 as a yellow crystalline solid.

IR (nujol): 3500 cm⁻¹, 3350 cm⁻¹ and 1682 cm⁻¹.

EXAMPLE 25

This Example illustrates the preparation of Compound 39 in Table I.

Concentrated hydrochloric acid (0.47 ml) and water (0.47 ml) were addedtogether to Compound 38 (600 mg) with constant stirring and the mixturecooled to 0° C. in an ice/salt bath. A solution of sodium nitrite (133mg) in water (0.3 ml) was added with stirring whilst maintaining thetemperature below 5° C.

A cuprous chloride solution was prepared by dissolving copper sulphate(6.25 g) and sodium chloride (1.625 g) in water (20 ml) and mixing 1.1mls of this solution with 2.2 mls of a solution prepared from sodiumbisulphate (2.65 g), sodium hydroxide (1.75 g) and water (20 ml).

The cuprous chloride solution (3.3 ml) was added slowly to the reactionmixture and small amounts of water added to wash solid material from thesides of the flask. The mixture was allowed to warm up to roomtemperature and then water added, followed by a basifying amount ofsodium bicarbonate solution. The solution was extracted into ethylacetate (2×30 ml) and the combined organic extracts washed withwater/brine, dried over magnesium sulphate and concentrated underreduced pressure to give a yellow oil. This oil was dissolved intrichloromethane, preabsorbed onto silica gel under reduced pressure andpassed down a silica column using 50/50 petrol/ether as eluent. Compound39 was isolated from the first two fractions by removing solvent underreduced pressure and recrystallising the product from a mixture ofpentane and ether.

NMR δ (CDCl₃): 7.53 (2H, s); 7.18 (1H, d); 6.97 (1H, m); 6.42 (1H, dd).

EXAMPLE 26

This Example illustrates the preparation of Compound 40 in Table I.

Step A

This describes the preparation of4-trifluoromethyl-1-(2,6-dichloro-4-ethoxycarbonylphenyl)-b 2-pyridone(Compound C). 3,5-Dichloro-4-fluorobenzotrifluoride (35 g, 0.15 mol) wasslowly added to concentrated sulphuric acid (120 ml) with stirring. Themixture was heated to 100° C. for 24 hours.

The reaction mixture was slowly poured onto ice (500 g) and the whitesolid which was formed was filtered off. The solid was dissolved indilute NaOH (2N) and the solution filtered before treating withconcentrated HCl to pH=1. A thick white precipitate was produced whichwas filtered. The solid was dissolved in ether (300 ml) and theremaining water separated. The organic layer was dried over magnesiumsulphate and evaporated in vacuo to give a white solid,3,5-dichloro-4-fluorobenzoic acid (27.6 g).

Melting Point: 194.5°-195.0° C.

NMR δ (CDCl₃, d₅ DMSO): 8.0 (2H, d).

Potassium carbonate (36 g, 0.26 moles) was added to a stirred mixture of3,5-dichloro-4-fluorobenzoic acid (27.6 g, 0.13 moles), ethyl iodide(41.2 g-0.26 moles) and dry dimethylformamide (300 ml) under nitrogen.The reaction was heated to 80° C. for 6 hours. The dimethylformamide wasremoved in vacuo and the residue treated with water (200 ml) acidifiedwith dilute hydrochloric acid and extracted with ethylacetate (2×250ml). The organic layer was washed with water, dried over magnesiumsulphate and evaporated in vacuo, to give an orange oil which waspurified by chromatography on silica, using a 4:1 mixture of petrol anddiethylether as eluent. The pink oil obtained crystallised on standing,and washing with ice-cold 40-60 petrol gave white crystals of ethyl3,5-dichloro-4-fluorobenzoate (29 g).

Melting Point: 59.5°-60.0° C.

NMR δ (CDCl₃): 1.40 (3H, t), 4.36 (2H, q), 8.00 (2H, d).

Sodium hydride (5.28 g of a 50% dispersion in mineral oil, 0.11 mol) waswashed with diethylether in a dry flask flushed with nitrogen. Drydimethylformamide (150 ml) was added and the mixture gently stirred atroom temperature, whilst 4-trifluoromethyl-1-pyridone (16.3 g, 0.1 mol)was added portionwise.

After 15 minutes, when the gas evaluation had ceased, ethyl3,5-dichloro-4-fluorobenzoate (29.0 g, 0.12 mol) was added, and thereaction was heated to 90° C. for 20 hours.

The dimethylformamide was removed in vacuo and the residue treated withwater (100 ml) and dilute HCl and extracted with ethylacetate (2×100ml). The combined organic portions were washed with water, dried overmagnesium sulphate and evaporated in vacuo. The residue was washed withan diethylether/petrol mixture to give a white solid which was purifiedfurther by recrystallization from a mixture of diethylether and petrolto give white crystals of 4-trifluoromethyl1-(2,6-dichloro-4-ethoxycarbonylphenyl)-2-pyridone (Compound C) (21.6g).

Melting Point: 126.7°-127.8° C.

NMR δ (d⁶ acetone): 1.40 (3H, t), 4.40 (2H, q), 6.65 (1H, dd), 6.97 (1H,m), 7.80 (1H, d, m), 8.20 (2H, s).

Step B

This describes the preparation of4-trifluoromethyl-1-(2,6-dichloro-4-formylphenyl)-2-pyridone (CompoundE).

A solution of potassium hydroxide [51 g (1.1 mol) in 50 ml of water] wasadded to a stirred solution of4-trifluoromethyl-1-(2,6-dichloro-4-ethoxycarbonylphenyl)-2-pyridone(Compound C) in ethanol [35 g (0.09 mol) in 500 ml of ethanol]. Thereaction was stirred for one hour at room temperature. The ethanolmixture was removed in vacuo and the residue treated with dilute HCl andextracted with ethylacetate (2×300 ml). The combined organic portions,were washed well with water, dried over magnesium sulphate andevaporated in vacuo to give a white solid of4-trifluoromethyl-1-(2,6-dichloro-4-carboxyphenyl)-2-pyridone (31.3 g).

Melting Point: 259°-260° C.

NMR δ (d⁶ acetone): 6.62 (1H, dd), 6.83 (1H, m), 7.76 (1H, d, m), 8.10(2H, s).

Borane (56 ml of a 1M solution in tetrahydrofuran (57 mmol) was addeddropwise to an ice cooled solution of4-trifluoromethyl-1-(2,6-dichloro-4-carboxyphenyl)-2-pyridone (10 g, 28mmol) in dry tetrahydrofuran (100 ml) under nitrogen. When the additionwas complete the reaction was stirred at 0° C. for 30 minutes, beforeallowing it to slowly warm up to room temperature, and continue stirringfor 5 hours. It was left to stand at room temperature overnight.

The reaction was thrown into a mixture of water (100 ml) and saturatedsodium bicarbonate solution (50 ml) and extracted with ethylacetate(2×100 ml). The combined organic extracts were washed with saturatedbicarbonate solution and water, dried over magnesium sulphate andevaporated in vacuo to leave a colourless oil, which solidified onstanding. Recrystallization from a mixture of petrol and ethylacetategave 4-trifluoromethyl-1-(2,6-dichloro-4-hydroxymethylphenyl)-2-pyridone(Compound D) (6.7 g).

Melting Point: 151.0°-151.5° C.

NMR δ (d⁶ acetone): 4.67 (2H, s), 6.52 (1 H, dd), 6.88 (1H, m), 7.54(2H, s), 7.66 (1H, d, m).

Dry dimethylsulphoxide in dry dichloromethane [1.25 ml (18 mmol) of DMSOin 4 ml of CH₂ Cl₂ ] was added dropwise to a well stirred solution ofoxalylchloride in dry dichloromethane (1.03 g of oxalylchloride (8.1mmol) in 20 ml of CH₂ Cl₂) at -60° C. in a flask that had been purgedwith nitrogen. When the addition was complete the reaction was stirredat -60° C. for ten minutes. The4-trifluoromethyl-1-(2,6-dichloro-4-hydroxyphenyl)-2-pyridone (CompoundD) (2.5 g, 7.4 mmol) in dry dichloromethane (5 ml) was added slowlydropwise at -60° C., and then stirred for 15 minutes. The triethylamine(5 ml, 37 mmol) was added dropwise, and after stirring at -60° C. foranother 10 minutes the reaction was slowly warmed up to roomtemperature.

The reaction was thrown into water (50 ml) and extracted withdichloromethane (2×100 ml). The combined organic portions were washedwith saturated sodium bicarbonate solution and then water, dried overmagnesium sulphate and evaporated in vacuo to give a yellow solid whichwas purified by chromatography on silica using a 2:1 mixture of petroland ethylacetate as eluent, to give4-trifluoromethyl-1-(2,6-dichloro-4-formylphenyl)-2-pyridone (CompoundE) (1.5 g).

Melting Point: 152.4°-153.5° C.

NMR δ (d⁶ acetone): 6.70 (1H, dd), 7.00 (1H, m), 7.82 (1H, d, m), 8.16(2H, s), 10.10 (1H, s).

Step C

A dry flask was flushed with nitrogen and charged with4-trifluoromethyl-1-(2,6-dichloro-4-hydroxymethylphenyl)-2-pyridone(Compound D) [0.73 g (2.2 mmol)] and dry dichloro-methane (15 ml). Theflask was cooled to -78° C. and diethylaminosulphurtrifluoride (0.31 ml,2.4 mmol) was added slowly dropwise. The reaction was stirred at -78° C.for 2 hours and then slowly allowed to warm up to room temperature. Thereaction was slowly added to a saturated solution of sodium hydrogencarbonate (20 ml) and extracted with ethyl acetate (2×30 ml). Thecombined organic layers were washed well with water, dried overmagnesium sulphate, and evaporated in vacuo to give a yellow solid whichwas chromatographed on silica with 50% petrol/diethyl ether as eluent.Recrystallisation from a mixture of pentane and diethylether gave4-trifluoromethyl-1-(2,6-dichloro-4-fluoromethylphenyl)-2-pyridone(Compound 40) (0.18 g)

Melting Point: 121.4°-122.0° C.).

NMR δ (d⁶ acetone): 5.36 (2H, s), 6.62 (1H, dd), 6.92 (1H, m), 7.70 (2H,m), 7.80 (1H, d, m).

EXAMPLE 27

This Example illustrates the preparation of Compound 13 in Table I.

4-Trifluoromethyl-1-(2,6-dichloro-4-difluoromethylphenyl)-2-pyridone(Compound 13) was prepared from Compound E as described in Example 26 bythe method described in Example 26 (Step C) except the reaction wascarried out at 0° C. When the addition of diethylaminosulphurtrifluoridewas complete the reaction was stirred at 0° C. for 11/2 hours.Recrystallization from petrol (40°-60° C. boiling range) gave therequired Compound 13.

Melting Point: 125.3°-126.0° C.

NMR δ (CDCl₃): 6.04, 6.66, 7.28 (1H, t), 6.44 (1H, dd), 7.00 (1H, m),7.20 (1H, d, m), 7.68 (2H, s).

EXAMPLE 28

This Example illustrates the preparation of4-trifluoromethyl-1-(2,6-dichloro-4-dichloromethylphenyl)-2-pyridone(Compound 14 in Table I).

4-Trifluoromethyl-1-(2,6-dichloro-4-formylphenyl)-2-pyridone (Compound Efrom Example 26) (1 g, 3 mmol) was added portionwise to a well stirredsolution of phosphorous pentachloride (0.68 g, 3.3 mmol) in carbontetrachloride (10 ml) at room temperature in a flask that had beenpurged with nitrogen. The reaction was stirred for 21/2 hours and thenleft to stand overnight. Additional phosphorous pentachloride was added,and stirring continued for another 6 hours until all the startingmaterial had been consumed.

The reaction was slowly added to a saturated solution of sodiumbicarbonate (30 ml) and extracted with ethylacetate (2×30 ml). Thecombined organic portions were washed with saturated bicarbonatesolution and water, dried over magnesium sulphate and evaporated to givean off white solid. Chromatography on silica using a 2:1 mixture ofpetrol and diethylether was eluent, followed by recrystallization from amixture of diethylether and pentane gave4-trifluoromethyl-1-(2,6-dichloro-4-dichloromethylphenyl)-2pyridone(Compound 14) (0.35 g).

Melting Point: 175.9°-176.8° C.

NMR δ (d⁶ acetone): 6.68 (1H, dd), 6.96 (1H, m), 7.30 (1H, s), 7.82 (1H,d, m), 7.98 (2 H, s).

EXAMPLE 29

This Example illustrates the preparation of4-trifluoromethyl-1-(2,6-dichloro-4-(1'-fluoro-1'-methylethylphenyl)-2-pyridone(Compound 41 in Table I).

A dry flask was flushed with nitrogen and charged with magnesium (0.42g, 17 mmol), dry ether (10 ml) and a crystal of iodine. 1 ml of asolution of methyliodide (2.5 g of methyliodide in 20 ml of dry ether)was added and when the iodine was decolourised the remainder was addeddropwise. The reaction was stirred at room temperature for 1 hour, andthen the4-trifluoromethyl-1-(2,6-dichloro-4-ethoxycarbonylphenyl)-2-pyridone(Compound C) (3 g, 7.9 mmol) in dry ether (40 mll) was added dropwise.The reaction was stirred for 1 hour at room temperature and was thenthrown into water (50 ml), acidified with dilute hydrochloric acid, andextracted with ethylacetate (2×40 ml). The combined organic extractswere washed well with water and brine, dried over magnesium sulphate andevaporated in vacuo to give a yellow oily solid. Chromatography onsilica, with 50% petrol/diethylether as eluent, followed byrecrystallisation from a mixture of ethylacetate and petrol (60°-80° C.boiling range) gave4-trifluoromethyl-1-(2,6-dichloro-4-(1'-hydroxy-1'-methylethylphenyl)-2-pyridone(1.6 g).

Melting Point: 149.4°-150.5° C.

NMR δ (d⁶ acetone): 1.6 (6H, s), 4.56 (1H, s), 6.60 (1H, dd), 6.92 (1H,m), 7.76 (1H, d, m), 7.76 (2H, s).

4-Trifluoromethyl-1-(2,6-dichloro-4-(1'-hydroxy-1'-methylethylphenyl)-2-pyridonewas treated with diethylaminosulphurtrifluoride as described in Example26 (Step C). Recrystallisation from a mixture of petrol (40°-60° C.boiling range) and diethylether gave a white compound,4-trifluoromethyl-1-(2,6-dichloro-4-(2'-fluoro-2'-methylethylphenyl)-2-pyridone(Compound 41) (0.4 g).

Melting Point: 173.6°-174.9° C.

NMR δ (d⁶ acetone): 1.76 (6H, d), 6.60 (1H, dd), 6.94 (1H, m), 7.72 (2H,s), 7.76 (1H, d, m).

The insecticidal activity of compounds of formula (I) is set out in thefollowing Table II as a grading of A, B or C where A indicates that80-100% mortality was observed, B indicates that 50-79% mortality wasobserved and C indicates that 0-49% mortality was observed. The testswere conducted by spraying a suitable support medium (e.g., leaves of asuitable food plant, or filter paper) with a solution of the compoundunder test and placing the pests thereon. Assessment of mortality wasmade 72 hours after spraying. In the test the compounds were used in theform of aqueous composition prepared by dissolving the compound inmixture of solvents consisting of 1 part by volume of acetone and 1 partby volume of ethanol and diluting the solution with water containing 1%by volume of a wetting agent (Synperonic "NX-Synperonic" is a RegisteredTrade Mark).

                  TABLE II                                                        ______________________________________                                               RATE OF AP-                                                            COM-   PLICATION                                                              POUND  ppm         NL     MD   BG   HV   CP   DB                              ______________________________________                                        1      500         C      C    C    C    C    C                               2      500         C      C    C    C    C    C                               3      500         C      C    C    C    C    C                               4      500         A      B    C    C    B    C                               5      500         C      A    C    C    A    C                               6      500         C      C    C    C    C    C                               7      500         C      A    B    C    C    C                               8      500         C      A    C    A    A    --                              9      500         C      B    C    C    C    C                               10     500         C      B    C    C    C    C                               11     500         A      C    C    C    C    --                              12     500         A      C    C    C    C    A                               13     500         A      A    C    A    --   A                               14     500         A      C    C    C    --   C                               16     500         A      B    C    C    --   C                               17     500         --     C    A    C    --   C                               20     500         C      A    C    C    C    C                               25     500         A      A    B    C    --   C                               27     500         C      C    B    C    --   C                               28     500         A      B    B    B    --   C                               29     500         --     A    A    C    --   C                               30     500         --     A    C    B    --   C                               31     500         --     A    A    C    --   C                               33     500         --     C    C    C    --   B                               34     500         --     C    A    C    --   C                               35     500         --     A    A    C    --   B                               36     500         --     B    C    C    --   C                               37     500         --     C    C    A    --   A                               40     500         B      C    C    C    --   C                               41     500         A      B    C    C    --   C                               ______________________________________                                    

                                      TABLE III                                   __________________________________________________________________________    CODE LETTERS         SUPPORT   TYPE OF                                                                             DURATION                                 (Table III)                                                                             TEST SPECIES                                                                             MEDIUM/FOOD                                                                             TEST  (days)                                   __________________________________________________________________________    NL        Nilaparvata lugens                                                                       Rice plants                                                                             CT    3                                                  (brown plant hopper)                                                CP        Chilo partellus                                                                          Oil seed rape                                                                           RT    3                                                  (maize stem bore)                                                                        leaf                                                     DB        Diabrotica balteata                                                                      Filter paper/                                                                           RT    3                                                  (rootworm larvae)                                                                        maize seed                                               BG        Blattella germanica                                                                      Plastic pot/                                                                            RT    3                                                  (cockrcach nymphs)                                                                       calf weenes                                                                   pellets                                                  MD        Musca domestica                                                                          Cotton wool/                                                                            CT    1                                                  (houseflies - adults)                                                                    sugar                                                    HV        Heliothis virescens                                                                      Cotton leaf                                                                             RT    3                                        __________________________________________________________________________

We claim:
 1. A compound of formula (V) ##STR17## wherein R¹, R², R⁴ andR⁵ are independently selected from hydrogen, halogen, lower alkyloptionally substituted by halogen, lower alkoxy optionally substitutedby halogen and lower alkenyl optionally substituted by halogen;R⁶ isoxygen or sulphur; R⁷ and R¹⁰ are independently selected from hydrogen,halogen, lower alkyl optionally substituted by halogen, lower alkoxyoptionally substituted by halogen, and lower thioalkoxy optionallysubstituted by halogen; R¹⁶ is formyl or R¹⁶ is hydrogen, halogen, loweralkyl optionally substituted by halogen or hydroxy, lower alkoxy, lowerthioalkoxy, cyano, nitro, oximino optionally substituted by lower alkyl,aryl, lower alkenyl or aralkyl wherein the aryl portion is optionallysubstituted with halogen or nitro; lower alkenyl, optionally substitutedby halogen or cyano; S(O)_(n) R¹¹ where n is 0, 1 or 2 and R¹¹ is loweralkyl optionally substituted by halogen; R¹⁷ is formyl, or R¹⁷ ishydrogen, or lower alkyl optionally substituted by halogen, loweralkenyl optionally substituted by halogen or CO₂ R¹² wherein R¹² islower alkyl optionally substituted by halogen; R¹⁸ is nitro, or C₁₋₆alkoxycarbonyl or lower alkyl substituted by hydroxy, or R¹⁸ is halogen,amino, mono- or di-(lower alkyl)-amino, lower alkyl substituted byhalogen, lower alkoxy optionally substituted by halogen and loweralkenyl optionally substituted by halogen, provided that R¹⁸ is notmonochloro- or monobromomethyl; and provided further that R¹⁶ is formylor R¹⁷ is formyl or R¹⁸ is nitro, or C₁₋₆ alkoxycarbonyl or lower alkylsubstituted by hydroxy; and that when R¹⁸ is trifluoromethyl and R¹ andR⁵ are halogen, R² and R⁴ are not both hydrogen; and that R⁷ R¹⁶, R¹⁷and R¹⁰ do not comprise from one to four halogen or trihalomethylsubstituents.
 2. A compound of formula (IIIA): ##STR18## wherein R¹⁹ istrihalomethyl andR²⁰ is an electrophilic group selected from nitro,lower thioalkoxy optionally substituted by halogen, formyl, and loweralkyl optionally substituted by halogen.